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[Development of novel solid-phase polymeric catalysts for organic syntheses].

Highly active and reusable polymeric catalysts were produced by a self-assembly process of non-cross-linked amphiphilic polymeric ligands with inorganic species. Thus a new insoluble tungsten polymeric catalyst PWAA 1 was prepared from H(3)PW(12)O(40) and poly[(N-isopropylacrylamide)-co-(acrylamide with ammonium salt)], which was suitable for the oxidation of alcohols, amines, and sulfides in aqueous hydrogen peroxide. A new insoluble palladium polymeric catalyst PdAS 2 was produced by self-organization of (NH(4))(2)PdCl(4) and poly[(N-isopropylacrylamide)(10)-co-diphenylphosphinostyrene], which is an excellent recyclable catalyst for the Suzuki-Miyaura reaction in water, water-organic solvents, and organic solvents. It is commercially available from Tokyo Kasei Kogyo (TCI). An improved insoluble palladium polymeric catalyst PdAS-V 3 was assembled from (NH(4))(2)PdCl(4) and poly[(N-isopropylacrylamide)(5)-co-diphenylphosphinostyrene], providing a reusable system for the Mizorogi-Heck reaction. A solid-phase titanium asymmetric polymeric catalyst TiSS 4 was made from Ti (O-i-Pr)(4) and poly(styryl-linked binaphtholate-co-styrene) which promotes an enantioselective carbonyl-ene reaction as a recyclable catalyst.

Catalysis↗

The role of radiolytically generated species in radiation-induced polymerization of vinylbenzyltrimethylammonium chloride (VBT) in aqueous solution: steady-state and pulse radiolysis study.

Radiation-induced polymerization of vinylbenzyltrimethylammonium chloride (VBT) in aqueous solution has been investigated by steady-state and pulse radiolysis techniques. The effects of dose, dose rate, monomer concentration, pH, and ambient conditions on steady state polymerization were investigated. The reactions of primary radicals of water radiolysis, such as OH radical, e(-)aq, and H atom, were studied. The reactions of other chemically active species such as O*-, oxidizing radicals such as N3*, Cl2(*-), Br(2*), SO4(*-), and a reducing specie such as CO2(*-) with VBT were also investigated. The reaction of VBT with OH radical and H atom were investigated by formation kinetics and by competition kinetics. The rate constant values for the reaction of OH radical with VBT were 4.7 x 10(9) dm3 mol(-1) s(-1) and 1.7 x 10(10) dm3 mol(-1) s(-1) by formation kinetics and by competition kinetics, respectively. The results indicate that OH radicals undergo electron transfer reactions (resulting in a radical cation) and addition reactions. The hydrated electron reacts with VBT with a rate constant of 1.9 x 10(10) dm3 mol(-1) s(-1) to form an anion. At pH approximately 1, H atom reaction with VBT is diffusion controlled with a rate constant of 5.1 x 10(9) dm3 mol(-1) s(-1) as determined by formation kinetics and 1.7 x 10(10) dm3 mol(-1) s(-1) as determined by competition kinetics. VBT radical anion reacts with VBT at a rate that is almost twice the rate at which VBT radical cation reacts with VBT, indicating anionic initiation of the polymerization of VBT. VBT undergoes very fast steady-state polymerization and dose rate; the presence of efficient radical quenchers such as oxygen and concentration of VBT in the aqueous solution affects the extent of polymerization. Typically, a dose of 4 kGy is sufficient to achieve 80-85% polymerization. The monomer solution shows a drastic increase in the viscosity of the solution, which finally gels to a soft rubbery mass.

Homeostasis↗

Do native and polymeric alpha1-antitrypsin activate human neutrophils in vitro?

BACKGROUND: alpha(1)-Antitrypsin (AAT)-Z deficiency is a risk factor for the development of COPD. Compared to wild-type M, AAT-Z has an increased tendency to polymerize, rendering it inactive as a serine proteinase inhibitor. It has been demonstrated that wild-type M- and Z-deficiency AAT polymers are chemotactic for human neutrophils. However, our own studies dispute a proinflammatory role for polymerized AAT-M and AAT-Z, suggesting rather that they are predominantly antiinflammatory, exhibiting inhibitory effects on lipopolysaccharide-stimulated human monocyte activation. The discrepancies between these observations prompted us to re-examine the effects of AAT. METHODS AND RESULTS: The effects of native and polymerized AAT-M and AAT-Z with varying levels of endotoxin contamination (0.08 to 2.55 endotoxin units [EU]/mg protein) on human neutrophil chemotaxis and interleukin (IL)-8 release, in vitro, were evaluated. Neither native nor polymerized (M- or Z-deficient) AAT contaminated with low levels of endotoxin (</= 0.08 EU/mg protein) stimulated neutrophil chemotaxis, whereas N-formyl methionyl leucyl phenylalanine (fMLP), a positive control, increased chemotaxis fourfold. A small but nonsignificant increase in neutrophil chemotaxis, however, was observed with AAT preparations containing higher levels of endotoxin (>/= 0.88 EU/mg protein), and significant chemotaxis occurred when AAT was spiked with either endotoxin or zymosan. In support, native and polymeric AAT-M with low endotoxin contamination completely inhibited neutrophil IL-8 release triggered by the zymosan, while AATs with high endotoxin contamination strongly induced IL-8 release and did not inhibit zymosan-stimulated IL-8 release. CONCLUSIONS: The proinflammatory effects of native and polymeric AAT may be critically dependent on the presence of other cell activators, bacterial or otherwise, while pure preparations of AAT appear to exert predominantly antiinflammatory activity.

Adult↗

Polymerization of actin in the absence and presence of cytochalasin B: problems of determining "critical concentration".

Various concentrations of actin (0.3 or 1 mM MgCl2, 1 mM ATP, 1 mM EGTA) reached their final degree of polymerization (measured by a pyrene dye attached to actin) earlier in the presence of cytochalasin B than in its absence. The curves relating concentrations of polymeric F-actin to total actin concentration were under these conditions highly nonlinear making an unambiguous extrapolation to zero F-actin concentration (to deduce the "critical concentration" of actin polymerization) impossible. The concentration of actin, above which polymerization occurred, was unaltered by cytochalasin B (although for reasons not yet understood the specific fluorescence intensity of polymerized actin was lower in the presence of cytochalasin B than in its absence). The results show that a distinct "critical concentration" of actin polymerization must not always be well defined.

Actins↗

Stimulation of actin polymerization by filament severing.

The extent and dynamics of actin polymerization in solution are calculated as functions of the filament severing rate, using a simple model of in vitro polymerization. The model is solved by both analytic theory and stochastic-growth simulation. The results show that severing essentially always enhances actin polymerization by freeing up barbed ends, if barbed-end cappers are present. Severing has much weaker effects if only pointed-end cappers are present. In the early stages of polymerization, the polymerized-actin concentration grows exponentially as a function of time. The exponential growth rate is given in terms of the severing rate, and the latter is given in terms of the maximum slope in a polymerization time course. Severing and branching are found to act synergistically.

Actin Depolymerizing Factors↗

Polymerization time for a microwave-cured acrylic resin with multiple flasks.

This study aimed at establishing the polymerization time of a microwave-cured acrylic resin (AcronTM MC), simultaneously processing 2, 4, and 6 flasks. Required time was measured according to the parameters: monomer release in water, Knoop hardness, and porosity. Samples were made with AcronTM MC in different shapes: rectangular (32 x 10 x 2.5 mm) for monomer release and porosity; and half-disc (30 mm in diameter x 4 mm in height) for Knoop hardness. There were four experimental groups (n = 24 per group): G1) one flask (control); G2) two flasks; G3) four flasks, and G4) six flasks. At first, polymerization protocol was similar for all groups (3 min/450 W). Time was then adjusted for G2, G3, and G4, based on monomer release evaluation in the control group, obtained by spectrophotometer Beckman DU-70, with emitting wave of 206 nm. Knoop hardness test was performed using a Shimadzu HMV 2000 hardness tester, and 10 indentations were performed on each specimen's surface. Porosity was assessed after specimens were immersed in black ink and the pores counted in a microscope. Results showed that the complete polymerization of the resin occurred in 4.5 min for two flasks (G2); 8.5 min for four flasks (G3); and 13 min for six flasks (G4), all with 450 W. Statistical analysis revealed that the number of flasks does not interfere with polymerization, Knoop hardness, and porosity of the resin. Results showed that polymerization of microwave-curing resin with more than one flask is a viable procedure, as long as polymerization time is adjusted.

Acrylic Resins↗

Dentine bond strength of a composite resin polymerized with conventional light and argon laser.

The use of argon laser (488 nm) has been suggested as a new alternative for polymerizing adhesive materials. This study aimed to evaluate the tensile bond strength of a microfilled composite (A110, 3M) inserted by incremental technique (3 increments of 1 mm) and by single increment (3 mm) polymerized by argon laser for 10, 20 and 30 seconds and halogen light for 40 seconds. Eighty (8 groups of 10 teeth) freshly extracted bovine teeth were stored in a freezer in distilled water for one week. The crowns were cross-sectioned from the roots. Pulpectomy was performed and the pulp chambers were sealed with wax. The buccal surfaces of the teeth were ground with wet sandpaper (grains: 120, 400, and 600) to expose the surface dentin, and the teeth were then included in acrylic resin. A metal device was used to fix each sample and a black propylene matrix25 (3 mm high with an internal millimetric delimitation) was used to insert the material according to the groups studied. The polymerization intervals were of 10, 20 and 30 seconds for the laser polymerization and 40 seconds for the conventional polymerization. Tensile tests were performed by a Universal Testing Machine 4442 (Instron) at a speed of 0.5 mm/min and 500 N load. According to the methodology used, the incremental technique increased bond strength values. There was no difference between the studied polymerization techniques when resin was filled in 3 increments.

Animals↗

Determination of polymeric aluminum in soil extracted with a modified anion-exchange resin as a solid-phase adsorbent by ICP-AES.

In the present work, a new method was established by applying solid-phase extraction (SPE) to preconcentrate and separate polymeric aluminum (Al) and using ICP-AES to determine the polymeric Al, the total monomeric Al, and the total Al in soil extracts, respectively. A modified resin was prepared with impregnated 8-hydroxyquinoline-5-sulfoxinate (HQS) on the anion-exchange resin. It has good recognition ability for Al fractions, compared to the commonly used cation ion-exchange resin, which has a better ability to adsorb cations and a weak ability to recognize detailed Al species. The optimum conditions for Al fractionation sorption, elution and separation and the interference of foreign ions were studied with the prepared resin by continuous column and batch procedures. Monomeric Al was bound to Pyrocathecol Violet (PCV) at pH 6.2, whereas the polymeric Al species did not react with PCV for at least 15 min. Because a stable complex of Al-PCV was not absorbed on the HQS modified resin, the polymeric Al could be preconcentrated on-line by the HQS-modified resin. The adsorbed polymeric Al was eluted with 3 mL of 3 mol L(-1) of HCl, and then detected by ICP-AES. The method has been applied to directly determine polymeric Al in soil extracts with high selectivity as well as a high preconcentration factor. It gives a limit of detection of 0.6 ng mL(-1) with a relative standard deviation of less than 5.7% (n = 5, 0.24 microg mL(-1) Al).

Journal Article↗

Polymeric micelles for drug delivery.

Polymeric micelles are nanoscopic core/shell structures formed by amphiphilic block copolymers. Both the inherent and modifiable properties of polymeric micelles make them particularly well suited for drug delivery purposes. An emphasis of this review has been placed on both the description and characterization techniques of the physical properties of polymeric micelles. Relevant properties discussed include micellar association, morphology, size and stability. These properties and characterization techniques are included to provide context for the known advantages and applications of polymeric micelles for drug delivery. The advantages and applications discussed include solubilization of poorly soluble molecules, sustained release and size advantages, and protection of encapsulated substances from degradation and metabolism. The three most widely studied block copolymer classes are characterized by their hydrophobic blocks, and are poly(propylene oxide), poly(L-amino acid)s and poly(ester)s. These three classes of block copolymers are reviewed with multiple examples of current research in which formulation techniques with polymeric micelles have been applied to some of the most challenging molecules in the pharmaceutical industry. The polymeric micelles used for drug delivery in these examples have shown the abilities to attenuate toxicities, enhance delivery to desired biological sites and improve the therapeutic efficacy of active pharmaceutical ingredients.

Amino Acids↗

[Three dimensional changes of the denture base of the complete denture following polymerization].

The objective of this study was to clarify some of the dimensional change patterns of the denture base of the complete denture following polymerization. Dimensional changes of three polymerization method types were compared. The complete dentures were measured by using the three dimensional measurement system. The results obtained were summarized as follows. 1. Dimensional changes from the original model immediately after polymerization of complete upper and lower dentures were recorded and all three polymerization methods produced shrinkage on all three axes toward the center. Heat cured resin samples and microwave cured resin samples showed the same shrinkage with pour type resin samples only showing 1/2 that amount. 2. The gradual dimensional changes occurring after polymerization up until 4 weeks were also recorded. The heat cured resin samples showed no additional changes but remained in its shrunken state. The pour-type resin samples began to enlarge until almost all of them reached the original model size within 4 weeks. The microwave cured resin samples began to enlarge but only slightly and then soon stopped changing. 3. All polymerization method types showed more dimensional change in the lower plate than in the upper plate.

Acrylic Resins↗

Influence of adhesive polymerization mode on dentin bond strength of direct core foundation systems.

This study examined the influence of various adhesive systems on dentin bond strength of direct core foundation resins. Two commercially available direct core foundation resin systems and 2 adhesive polymerization modes were used. Facial bovine dentin surfaces were wet ground on 600-grit SiC paper. Dentin surfaces were treated according to the manufacturers' instructions and were light polymerized (control). Chemical- and light-polymerized adhesive systems were used separately. The resin paste was condensed into a mold and bonded to the dentin surface. Ten specimens per test group were stored in water at 37 degrees C for 24 hours, and a shear test was conducted at a crosshead speed of 1.0 mm/minute using a universal testing machine. Analysis of variance (ANOVA) and Duncan's multiple comparison test were performed (alpha = 0.05). Dual polymerization of resin pastes revealed higher bond strength with the combination of light-polymerized adhesive (22.8-24.3 MPa), but significantly lower bond strength with the combination of a chemical-polymerized adhesive (4.2-5.7 MPa). The present data suggests that dentin bond strengths in direct core foundation systems can be influenced by the combination of adhesive and resin paste.

Animals↗

Effect of anti-beta2glycoprotein I Lupus Anticoagulants on fibrin polymerization and fibrinolysis.

Anti-beta2-Glycoprotein I (beta2GPI) autoantibodies are the prominent laboratory feature of Hughes syndrome. By prolonging some coagulation tests in the presence of exogenous phospholipids (PL), they behave as classical Lupus Anticoagulants (LA). We investigated the effect of 3 affinity-purified anti-beta2GPI IgG preparations from patients with Hughes syndrome on fibrin polymerization and fibrinolysis of normal plasma, measured by comparing the optical densities of assay mixtures in the presence of the autoantibodies or normal IgG. The presence of anti-beta2GPI IgG in diluted Russell Viper Venom Time (dRVVT) assays, carried out using a PL dilution of 1:8 or 1:64, resulted in a delay in the onset of polymerization by 30-40 and 60-70s, respectively. Fibrin polymerization was complete after 250s for both anti-beta2GPI IgG and normal IgG. The inhibitory effect of the anti-beta2GPI antibodies was not observed in the presence of excess PL, as expected for LA. Anti-beta2GPI IgG increased the plateau level of polymerization when dRVVT was performed in the presence of 1.5 nM recombinant tissue plasminogen activator, but did not impair the fibrinolytic process, which was almost complete after 250 min. The autoantibodies did not delay the onset of fibrin polymerization in tests carried out using recombinant tissue factor. On the contrary, the autoantibodies enhanced polymerization in prothrombin time assays, and accelerated it in tissue thromboplastin inhibition tests, with no effect on fibrinolysis. These data provide evidence that anti-beta2GPI LA may act as either anticoagulants or procoagulants in different in vitro coagulation tests.

Adolescent↗

Enhancement of erythrocyte sedimentation rate by polymerized hemoglobin.

Development of hemoglobin-based blood substitutes requires the scrutiny of blood rheological parameters that could be influenced by this class of molecules. Accordingly, we have examined the effects of glutaraldehyde-polymerized human hemoglobin on the erythrocyte sedimentation rate (ESR). For this purpose, human hemoglobin (Hb) was polymerized by glutaraldehyde, and its progress was monitored by gel permeation. ESR was measured by addition of hemoglobin or polymerized Hb (Poly-Hb) to citrated rat whole blood. The results indicate that, whereas Hb exerted minimal perturbation of ESR, Poly-Hb obtained under some polymerization conditions induced an over fifty-fold elevation of ESR. When polymerized Hb was fractionated by size, and different fractions were tested for their effects on ESR, a sharp dependence of ESR enhancement on molecular size of polymerized Hb was found. These observations suggest that ESR enhancement is mediated by macromolecular bridging formed by Poly-Hb of an adequate length between the surfaces of two stacking erythrocytes.

Blood Sedimentation↗

Polymerization color changes of esthetic restoratives.

The color changes of three different types of tooth-colored restoratives during polymerization were investigated using colorimetry. L*, a*, b* color parameters of five different shades of Z100 (a mini-filled composite resin), Fuji II LC (a resin-modified glass-ionomer cement), and Dyract (a polyacid-modified composite resin) were taken precure and postcure. The results showed that the restoratives evaluated all underwent color changes during polymerization. The polymerization changes in color parameters were shade and not material dependent. Changes in L* parameter or lightness during polymerization were significant for all material and shade combinations and had the greatest influence on the overall polymerization color change. As the color change was perceivable by the human eye for most shades of materials, the clinical practice of polymerizing some material on, or adjacent to, the undried tooth to confirm shades of esthetic restoratives before restorative procedures is prudent.

Colorimetry↗

Microhardness of resin composites polymerized by plasma arc or conventional visible light curing.

This study evaluated the effectiveness of the plasma arc curing (PAC) unit for composite curing. To compare its effectiveness with conventional quartz tungsten halogen (QTH) light curing units, the microhardness of two composites (Z100 and Tetric Ceram) that had been light cured by the PAC or QTH units, were compared according to the depth from the composite surface. In addition, linear polymerization shrinkage was compared using a custom-made linometer between composites which were light cured by PAC or QTH units. Measuring polymerization shrinkage for two resin composites (Z100 and Tetric Ceram) was performed after polymerization with either QTH or PAC units. In the case of curing with the PAC unit, the composite was light cured with Apollo 95E for two (Group 1), three (Group 2), six (Group 3) or 2 x 6 (Group 4) seconds. For light curing with the QTH unit, the composite was light cured for 60 seconds with Optilux 500 (Group 5). The linear polymerization shrinkage of composites was determined in the linometer. Two resin composites were used to measure microhardness. Two-mm thick samples were light cured for three seconds (Group 1), six seconds (Group 2) or 12 (2 x 6) seconds (Group 3) with Apollo 95E or they were conventionally light cured with Optilux 500 for 30 seconds (Group 4) or 60 seconds (Group 5). For 3 mm thick samples, the composites were light cured for six seconds (Group 1), 12 (2 x 6) seconds (Group 2) or 18 (3 x 6) seconds (Group 3) with Apollo 95E or they were conventionally light cured with Optilux 500 for 30 seconds (Group 4) or 60 seconds (Group 5). Twenty samples were assigned to each group. The microhardness of the upper and lower surfaces was measured with a Vickers hardness-measuring instrument under load. The difference in microhardness between the upper and lower surfaces in each group was analyzed by paired t-test. For the upper or lower surfaces, one-way ANOVA with Tukey was used. For Tetric Ceram, the amount of polymerization shrinkage was lower when cured with the Apollo 95E for two or three seconds than when cured for six and 12 (2 x 6) seconds, or for 60 seconds with Optilux 500 (p<0.05). For Z100, the amount of linear polymerization shrinkage was lower when cured with the Apollo 95E for two, three and six seconds than for 12 (2 x 6) seconds with Apollo 95E or for 60 seconds with the Optilux 500 (p<0.05). The results of the microhardness test indicated that there was no statistically significant difference in microhardness between groups for the upper surface. However, for the lower surface, when the composites were light cured with Apollo 95E for three seconds as recommended by the manufacturer, microhardness of the lower surface was usually lower than that of the upper surface and did not cure sufficiently. Conclusively, when compared with conventional QTH unit, the PAC unit, Apollo 95E did not properly cure the lower composite surface when the layer thickness exceeded 2 mm. In addition, three seconds of curing time, which the manufacturer recommended, was insufficient for optimal curing of composites.

Analysis of Variance↗

Post-gel shrinkage with pulse activation and soft-start polymerization.

This study investigated the influence of pulse activation and soft-start polymerization regimens on the post-gel shrinkage of a visible light-activated composite resin (Z100). A light-cure unit (BISCO VIP) that allowed for independent command over time and intensity was used. The six light-curing modes that were examined include: Control (C)-400 mW/cm2 [40 seconds]; Pulse Delay I (PDI)-100 mW/cm2 [3 seconds], delay [3 minutes], 500 mW/cm2 [30 seconds]; Pulse Delay II (PDII)-200 mW/cm2 [20 seconds], delay [3 minutes], 500 mW/cm2 [30 seconds]; Soft-start (SS)-200 mW/cm2 [10 seconds], 600 mW/cm2 [30 seconds]; Pulse Cure I (PCI)--two 400 mW/cm2 [10 seconds] and one 400 mW/cm2 [20 seconds] pulses with 10 seconds interval between; and Pulse Cure II (PCII)-two 400 mW/cm2 [20 seconds] pulses with 20 seconds interval between. A strain-monitoring device measured the linear polymerization shrinkage associated with the various cure modes during and post light polymerization up to 60 minutes. Five specimens were made for each cure mode. Data was analyzed using one-way ANOVA and Scheffe's post-hoc test at significance level 0.05. Post-gel shrinkage associated with PDI was significantly lower than with PDII, SS and PCI immediately post light-polymerization. At one-minute post light polymerization, PDI had significantly lower shrinkage compared to PDII and SS. Significant differences in shrinkage were observed between PDI and SS only at 10, 30 and 60 minutes. At all time intervals, no significance in post-gel shrinkage was observed between the control and all-pulse activation/soft-start polymerization regimens.

Analysis of Variance↗

[Advances of polymeric materials applied in TCM preparation and separation].

In this paper, the advance of polymeric materials applied in the development of traditional Chinese medicine (TCM) and natural products was reviewed. Especially the research progresses in use of the polymeric membranes, polymeric flocculating agents, polymeric sorbents and polymeric drug delivery system (DDS) in the separation and preparation of herb and TCM were discussed in details. In addition, the future develorment of polymeric materials in TCM preparation was also discussed.

Administration, Cutaneous↗

Improved diagnostics: clinical evaluation of a color-coded, polymeric periodontal probe.

The objective of this study was to compare the accuracy, reproducibility and patient comfort of a newly designed, color-coded, polymeric periodontal probe to a traditional, color-coded metal probe. Twenty-four adult subjects with varying degrees of periodontal disease (from slight to severe) reported for two visits, one week apart. A randomization schedule for probe use was adopted over the two visits so that the gingival crevices in two quadrants were probed with the same probe (metal or polymeric) providing reproducibility information for each probe, while the other two quadrants were probed first with one probe then the other for comparison data yielding information on accuracy. A bleeding index was obtained using the same schedule. Clinical scoring was performed by the same examiner. After probing each quadrant, subjects rated discomfort using a visual analog scale (VAS). Results showed no significant difference in depth readings greater than 2 mm between the polymeric and metal probes (3.41 +/- 0.37 mm vs. 3.38 +/- 0.32 mm, p = 0.55). Significantly less discomfort (assessed by VAS) was recorded by patients after polymeric probe use (3.70 +/- 2.40 cm vs. 4.44 +/- 2.49 cm, p = 0.015). The bleeding index indicated significantly less bleeding with the polymeric probe (0.80 +/- 0.56 vs. 1.24 +/- 0.65, p = 0.0001). Both the polymeric and metal probes were found to produce highly reproducible results in all measures across visits.

Adult↗